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Related Concept Videos

[3,3] Sigmatropic Rearrangement of 1,5-Dienes: Cope Rearrangement01:21

[3,3] Sigmatropic Rearrangement of 1,5-Dienes: Cope Rearrangement

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The Cope rearrangement is classified as a [3,3] sigmatropic shift in 1,5-dienes, leading to a more stable, isomeric 1,5-diene. The reaction involves a concerted movement of six electrons, four from two π bonds and two from a σ bond, via an energetically favorable chair-like transition state.
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Photochemical Electrocyclic Reactions: Stereochemistry01:26

Photochemical Electrocyclic Reactions: Stereochemistry

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The absorption of UV–visible light by conjugated systems causes the promotion of an electron from the ground state to the excited state. Consequently, photochemical electrocyclic reactions proceed via the excited-state HOMO rather than the ground-state HOMO. Since the ground- and excited-state HOMOs have different symmetries, the stereochemical outcome of electrocyclic reactions depends on the mode of activation; i.e., thermal or photochemical.
Selection Rules: Photochemical Activation
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Thermal and Photochemical Electrocyclic Reactions: Overview01:26

Thermal and Photochemical Electrocyclic Reactions: Overview

2.9K
Electrocyclic reactions are reversible reactions. They involve an intramolecular cyclization or ring-opening of a conjugated polyene. Shown below are two examples of electrocyclic reactions. In the first reaction, the formation of the cyclic product is favored. In contrast, in the second reaction, ring-opening is favored due to the high ring strain associated with cyclobutene formation.
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Cycloaddition Reactions: MO Requirements for Photochemical Activation01:12

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Some cycloaddition reactions are activated by heat, while others are initiated by light. For example, a [2 + 2] cycloaddition between two ethylene molecules occurs only in the presence of light. It is photochemically allowed but thermally forbidden.
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Cycloaddition Reactions: Overview01:16

Cycloaddition Reactions: Overview

3.3K
Cycloadditions are one of the most valuable and effective synthesis routes to form cyclic compounds. These are concerted pericyclic reactions between two unsaturated compounds resulting in a cyclic product with two new σ bonds formed at the expense of π bonds. The [4 + 2] cycloaddition, known as the Diels–Alder reaction, is the most common. The other example is a [2 + 2] cycloaddition.
3.3K
[3,3] Sigmatropic Rearrangement of Allyl Vinyl Ethers: Claisen Rearrangement01:24

[3,3] Sigmatropic Rearrangement of Allyl Vinyl Ethers: Claisen Rearrangement

2.7K
The Claisen rearrangement is a [3,3] sigmatropic rearrangement of allyl vinyl ethers to unsaturated carbonyl compounds. The rearrangement is a concerted pericyclic reaction proceeding via a chair-like transition state.
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Updated: Jan 13, 2026

Cercosporin-Photocatalyzed [4+1]- and [4+2]-Annulations of Azoalkenes Under Mild Conditions
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Alkynyltriazenes in Photochemical Metal-Free Doyle-Kirmse Rearrangements.

Ningning Liu1, Linus Bjarne Dittmer2, Melina Maag1

  • 1Organisch-Chemisches Institut, Heidelberg University, Im Neuenheimer Feld 270, Heidelberg, 69120, Germany.

Angewandte Chemie (International Ed. in English)
|January 10, 2026
PubMed
Summary
This summary is machine-generated.

This study introduces a novel photochemical method for Doyle-Kirmse rearrangement reactions using alkynyl triazenes. This approach efficiently synthesizes valuable α-mercapto-nitriles, offering a safer and more versatile alternative for generating C─C and C─S bonds.

Keywords:
CyanocarbenesNitrile compoundsPhotochemistryRearrangementTriazenes

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Area of Science:

  • Organic Chemistry
  • Synthetic Methodology
  • Photochemistry

Background:

  • Doyle-Kirmse rearrangement reactions are crucial for forming C─C and C─S bonds.
  • Cyanocarbene-involved Doyle-Kirmse reactions are underexplored due to precursor synthesis and reactivity challenges.

Purpose of the Study:

  • To develop a novel photochemical strategy for Doyle-Kirmse rearrangement reactions involving cyanocarbenes.
  • To enable the synthesis of α-mercapto-nitriles from alkynyl triazenes under metal- and additive-free conditions.

Main Methods:

  • Photochemical rearrangement of alkynyl triazenes.
  • Generation of intermediate cyanocarbenes.
  • Metal- and additive-free reaction conditions.

Main Results:

  • Successful synthesis of α-mercapto-nitriles in moderate-to-good yields.
  • Access to highly substituted stereogenic carbon centers.
  • Demonstrated broad substrate compatibility with allylsulfides, propargyl sulfides, and allenyl sulfides.
  • Successful upscaling of the reaction.

Conclusions:

  • The developed photochemical method provides a safe and efficient route to α-mercapto-nitriles.
  • This approach expands the scope of Doyle-Kirmse rearrangement reactions involving cyanocarbenes.
  • The transformation offers significant synthetic potential due to mild conditions and broad applicability.